CN1745050A - Tricyclopenta-triphenylene and preparing method thereof - Google Patents
Tricyclopenta-triphenylene and preparing method thereof Download PDFInfo
- Publication number
- CN1745050A CN1745050A CNA2004800032191A CN200480003219A CN1745050A CN 1745050 A CN1745050 A CN 1745050A CN A2004800032191 A CNA2004800032191 A CN A2004800032191A CN 200480003219 A CN200480003219 A CN 200480003219A CN 1745050 A CN1745050 A CN 1745050A
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- China
- Prior art keywords
- straight
- branched
- carbonatoms
- alkyl
- substituting group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 160
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 239000012776 electronic material Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 138
- 125000000217 alkyl group Chemical group 0.000 claims description 93
- -1 imino-methylene Chemical group 0.000 claims description 90
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 125000005843 halogen group Chemical group 0.000 claims description 58
- 229920006395 saturated elastomer Polymers 0.000 claims description 53
- 150000003839 salts Chemical class 0.000 claims description 45
- 238000002360 preparation method Methods 0.000 claims description 40
- 125000002837 carbocyclic group Chemical group 0.000 claims description 34
- 125000000623 heterocyclic group Chemical group 0.000 claims description 34
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 25
- 150000002367 halogens Chemical class 0.000 claims description 25
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 23
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 22
- 125000005842 heteroatom Chemical group 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 125000004423 acyloxy group Chemical group 0.000 claims description 19
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 19
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 19
- 125000005115 alkyl carbamoyl group Chemical group 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 125000003282 alkyl amino group Chemical group 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 claims description 12
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 12
- 125000003368 amide group Chemical group 0.000 claims description 12
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 125000006239 protecting group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010168 coupling process Methods 0.000 claims description 9
- 230000026030 halogenation Effects 0.000 claims description 9
- 238000005658 halogenation reaction Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 239000003504 photosensitizing agent Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229920001197 polyacetylene Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 claims description 2
- 230000009920 chelation Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 abstract description 24
- 229910003472 fullerene Inorganic materials 0.000 abstract description 24
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- WOYKPMSXBVTRKZ-UHFFFAOYSA-N sumanene Chemical compound C1=C(C2=C34)CC3=CC=C(C3)C4=C4C3=CC=C(C3)C4=C2C3=C1 WOYKPMSXBVTRKZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000007385 chemical modification Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 125000001743 benzylic group Chemical group 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000002585 base Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- VXRUJZQPKRBJKH-UHFFFAOYSA-N corannulene Chemical group C1=CC(C2=C34)=CC=C3C=CC3=C4C4=C2C1=CC=C4C=C3 VXRUJZQPKRBJKH-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000006519 Mcmurry reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N pentadiene group Chemical class C=CC=CC PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- JWQKMEKSFPNAIB-SNVBAGLBSA-N (5r)-1-methyl-5-prop-1-en-2-ylcyclohexene Chemical compound CC(=C)[C@@H]1CCC=C(C)C1 JWQKMEKSFPNAIB-SNVBAGLBSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- PXACTUVBBMDKRW-UHFFFAOYSA-N 4-bromobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Br)C=C1 PXACTUVBBMDKRW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- UXZIDIYMFIBDKT-UHFFFAOYSA-N Sylvestrene Natural products CC(=C)C1CCCC(C)=C1 UXZIDIYMFIBDKT-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000001589 carboacyl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/50—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/123—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of only one hydrocarbon
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- C07C2531/22—Organic complexes
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- C07C2531/24—Phosphines
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- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
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Abstract
The invention provides sumanene and derivatives thereof and a process for the production of both. As represented by the scheme (1), benzotris- (norbornadiene) (87) is synthesized from norbornadiene (86) and then converted by metathesis into hexahydrosumanene (88) and the heaxahydrosumanene (88) is dehydrogenated into sumanene (84). Thus, sumanene can be mass-produced under mild conditions. Further, sumanene analogues wherein the carbon atoms at the benzylic positions are replaced by nitrogen (N) or oxygen (O) can be also similarly produced and various derivatives can be obtained by further chemical modification of such analogues. Sumanene and analogues and derivatives thereof are extremely useful as the raw material for the synthesis of electronic materials, various fullerenes, and heterofullerenes, and so on.
Description
Technical field
The present invention relates to a kind of three cyclopenta triphenylenyl (Sumanene) and preparation method thereof.
Background technology
With C
60(following formula (82)) and C
70Headed by various soccerballenes and the such one group of carbon homologue of carbon nanotube (below it being commonly referred to as " fullerene "), become noticeable New Times material owing to it has special rerum natura.Except C
60And C
70In addition, known fullerene also has various structures, has its inherent rerum natura separately.The whole world is all carried out chemical modification in active research with it, makes it obtain more various function.
But the preparation method of fullerene is only limited to so-called arc discharge method etc., C at present
60And C
70Become more readily available, but can only produce very other fullerene of trace, be very difficult to obtain, thereby, even the fullerene chemical modification is made the high performance material of various structures, the problem that also can exist the kind of starting raw material to lack.
In view of the foregoing, the chemosynthesis fullerene of attempting in vogue all over the world, these researchs just are on the scent finally, but whom does not also have achieve success.But, different according to the method for Synthetic Organic Chemistry with above-mentioned arc discharge method etc., the molecular structure of product can freely be controlled, therefore mainly continue research and just can expect freely to obtain to be difficult at present the fullerene that obtains.And then we think and are not limited to existing fullerene, if can synthesize new fullerene and derivative thereof, just can open up new prospect at the design aspect of novel material.For example, use the assorted fullerene of the part of heteroatoms substituted fullerene class carbon atom, in theory research, be concerned by people very much (for example reference " M.Riad Manaa; David W.Sprehn, and Heather A.Ichord, J.Am.Chem.Soc.; 2002,124, p.13990-13991."), but except C59N (with reference to " and Science, 1995,269, p.1554.") etc. the compound of few part, all also do not prepare up to now, expect that its vitochemical synthetic method can establish.
Now, for the synthetic C that contains
60Part-structure be the compound of on-plane surface conjugated system carbon skeleton and studying.But, up to now, have only the report title to synthesize compound (following formula (83)) and the derivative thereof that is Corannulene in 1966, but also just under laboratory level, synthesize.
Corannulene is as containing above-mentioned C
60Part-structure compound and synthesized first in the world, its academic significance is very big.And then, the approach that also had report describe in 1999 to synthesize Corannulene under can the mitigation condition in flask relatively largely (Andrzej Sygulaand Peter W.Rabideau, J.Am.Chem.Soc., 2000,122, p.6323-6324.).But Corannulene has problem during as the synthesis material of fullerene etc.Its reason is that all on phenyl ring, its reactivity is so not high for the carbon atom of its skeleton.Therefore, can also be only limited to very limited structure by synthetic Corannulene derivative now, and then can expect to be incorporated into C
60Deng also very difficult in the compound.
Summary of the invention
Thereby, the object of the present invention is to provide a kind of compound that can in the synthesis material of fullerene and assorted fullerene etc., use and the preparation method of derivative thereof.
In order to address the above problem, the invention provides new compound, its tautomer and steric isomer and their salt of following general formula (1) expression.
In the formula, A
1～A
6Can be respectively identical or different, for hydrogen atom, straight or branched alkyl or aromatic hydrocarbyl, at A
1～A
6On when having the hydrogen atom of benzyl position, its hydrogen atom can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different, for halogen, straight chain shape or the low molecule of a catenate or macromolecular chain (can contain heteroatoms, also can not contain heteroatoms in its main chain and the side chain, unsaturated link(age) can be contained, also unsaturated link(age) can be do not contained, can contain ring texture, also can not contain ring texture), (it can be monocycle or condensed ring for carbocyclic ring or heterocycle, it can be saturated or undersaturated ring, can have substituting group, also can not have substituting group), electron-donating group or electron-withdrawing group, perhaps be attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
X
1～X
3Be respectively identical or different, be methylene radical (following formula (2)), vinylidene base (following formula (3)), carbonyl (following formula (4)), thiocarbonyl (following formula (5)), imino-methylene radical (following formula (6)), imino-(following formula (7)) or Sauerstoffatom (following formula (8)), X
1～X
3On when having hydrogen atom, its hydrogen atom also can replace with substituting group,
Above-mentioned X
1～X
3On substituting group be respectively identical or different, for halogen, straight chain shape or the low molecule of a catenate or macromolecular chain (can contain heteroatoms, also can not contain heteroatoms in its main chain and the side chain, unsaturated link(age) can be contained, also unsaturated link(age) can be do not contained, can contain ring texture, also can not contain ring texture), (it can be monocycle or condensed ring for carbocyclic ring or heterocycle, it can be saturated or undersaturated ring, can have substituting group, also can not have substituting group), electron-donating group or electron-withdrawing group, perhaps be attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together.
Description of drawings
Fig. 1 is the UV-VIS spectrogram of three cyclopenta triphenylenyl, and the solvent that uses is CHA.
Fig. 2 is the UV-VIS spectrogram of three cyclopenta triphenylenyl, and the solvent that uses is THF.
Fig. 3 is the UV-VIS spectrogram of three cyclopenta triphenylenyl, and the solvent that uses is CH3CN.
Fig. 4 is the UV-VIS spectrogram of three cyclopenta triphenylenyl, and the solvent that uses is CH
2Cl
2
Fig. 5 is that whole spectrograms of Fig. 1～4 are summarised among 1 figure.
Embodiment
Specify the present invention below.
The noticeable chemical structure of except that Corannulene another has the structure (following formula (84)) that is known as three cyclopenta triphenylenyl.Corannulene contains C
60C
5The symmetric part skeleton, and three cyclopenta triphenylenyl contain C
60C
3The symmetric part skeleton.And three cyclopenta triphenylenyl are different with Corannulene, are primarily characterized in that the carbon that contains the benzyl position on 3 positions.
In general, make synthetic its price height of raw material to contain benzyl position carbon compound.Its reason is that benzyl position carbon activity is very high, can produce various spikes such as positively charged ion kind, negatively charged ion kind, sylvestrene, these spikes further can be applied in conjunction with formation reaction.Thereby the reactivity of three cyclopenta triphenylenyl for example, is thought and can be synthesized multiple derivative by the various functional groups of direct introducing such as oxidizing reaction of benzyl position far above Corannulene.And further expectation is that raw material can synthesize not the just all cpds of fullerene with these derivatives.
And the carbon that contains the benzyl position not only helps as synthesis material, and the utility value of above-mentioned active body self is also big.For example, think that it has the interior bag ability of metal etc. because the benzyl negatively charged ion kind of three cyclopenta triphenylenyl contains the structure same with cyclopentadienyl.Thereby not only this active body originally utilizes possibility big on industry, can also expect it uses compound as the model research of bag type fullerene compound in the metal development.
So, three cyclopenta triphenylenyl are very big in learned value, and the utility value on industry is also very big, and many researchists are devoted to study the synthetic of it.But may there be successful synthetic report so far because its molecular shape change is bigger.The document of describing three cyclopenta triphenylenyl is many, but each piece of writing all stop at Theoretical Calculation etc. (for example with reference to " U.DevaPriyakumar and G.Narahari Sastry; J.Phys.Chem.A; 2001,105, p.4488-4494. " and " U.Deva Priyakumar and G.Narahari Sastry; TetrahedronLetters; 2001,42, p.1379-1381. ").
In addition, be synthesized (Koichi Imamura, Kazuo Takimiya of the compound (following formula (85)) that replaces with sulphur atom of the benzyl position carbon of three cyclopenta triphenylenyl, Yoshio Asoand Tetsuo Otsubo, Chem.Commun., 1999, p.1859-1860.).This compound itself is very significant compound, but its synthetic now must be under vacuum carrying out under 1000 ℃ the stringent condition, and mass production reaches relatively difficulty of industrialization level.And the rerum natura difference of itself and three cyclopenta triphenylenyl is very big after all.For example the reactivity of above-mentioned sulphur atom can be not free as the carbon of benzyl position, and what can expect can only be to add oxygen base etc.Therefore, though can reckon with the chemical structure and the favourable purposes of three cyclopenta triphenylenyl, do not synthesize the successful example of aspect so far.
The inventor successfully synthesizes three cyclopenta triphenylenyl in the world first.Then, the The compounds of this invention (i.e. three cyclopenta triphenylenyl and derivatives thereof) and its preparation method of following formula (1) expression have been established.
Compound, its tautomer or the steric isomer of above-mentioned general formula (1) expression or the preparation method of their salt are not particularly limited, and can prepare by any method, the following describes preferred preparation method of the present invention.According to this preparation method, can use the method for Synthetic Organic Chemistry to obtain three cyclopenta triphenylenyl and derivatives thereof simply.For example for parent compound three cyclopenta triphenylenyl, can be shown in following equation 1, from cheaply and the norbornadiene that obtains easily (following formula (86)), in flask, under the demulcent condition, only synthesize with 3 steps.
Reaction conditions
A) BuLi, t-BuOK, BrCH
2CH
2Br, THF ,-78 ℃～-45 ℃ CuI next, room temperature
B) (the PCy of catalytic amount
3)
2RuCl
2=CHPh, CH
2=CH
2, toluene, 0 ℃～80 ℃
C) DDQ, toluene, 110 ℃
Specify the preparation method of the invention described above below.That is, at first prepare the compound of following formula (76) expression.This compound and its salt are the new compounds that the inventor invents, and can change into three cyclopenta triphenylenyl and derivatives thereof through peroxidation (dehydrogenation) reaction again.
In the formula, R
1～R
6Be respectively identical or different, be the alkyl or the aromatic hydrocarbyl of hydrogen atom, straight or branched, be preferably hydrogen atom, carbonatoms and be alkyl, the phenyl or naphthyl of 1～6 straight or branched.X
11, X
21And X
31Be respectively identical or different, for methylene radical, imino-or Sauerstoffatom, when it was imino-, its hydrogen atom also can replace with protecting group.The following describes the preparation method of this compound.
The compound of following formula (76) expression and the preparation method of salt thereof are not particularly limited, but are more preferably the preparation method of the replacement(metathesis)reaction of the compound that comprises following formula (77) expression.This preparation method is the new preparation method that the inventor invents.Replacement(metathesis)reaction is well-known reaction, and the inventor finds the compound that it can be applicable to following formula (77) expression.By the invention of this method, the acquisition of three cyclopenta triphenylenyl and derivative thereof has become simply.
In the formula, R
1～R
6, X
11, X
21And X
31Respectively with following formula (76) in identical.
The condition of above-mentioned replacement(metathesis)reaction is not particularly limited, and can equally with existing replacement(metathesis)reaction carry out, but the preferred catalyzer that uses carries out.Above-mentioned catalyzer is not particularly limited, and can use normally used so-called displacement catalyzer, can use separately, also can two kinds or more kinds of being used in combination.And above-mentioned catalyzer more preferably contains at least a element that is selected from for example ruthenium, aluminium, titanium, molybdenum and the tungsten.In the above-mentioned displacement catalyzer, the catalyzer that particularly contains ruthenium and molybdenum of present more exploitation.As the above-mentioned catalyzer that uses among the present invention, particularly, especially preferably contain and be selected from for example (PCy
3)
2RuCl
2Promptly two (thricyclohexyl phosphino-) Ben Yajiaji ruthenium (II) muriates of=CHPh, Al (C
2H
5)
3-TiCl
4, Al (C
2H
5)
3-MoCl
3And Al (C
2H
5)
3-WCl
6In at least a catalyzer, but be not limited to this.The usage quantity of above-mentioned catalyzer also is not particularly limited, and can adjust aptly according to reaction efficiency and cost etc., for example preferably below so-called stoichiometry.The usage quantity that is fit to of above-mentioned catalyzer changes according to the kind of catalyzer and reaction scale etc., does not have certain regulation, but in the reaction of flask level, for example is about 5mol% with respect to following formula (77) expression compound.In addition, in general, catalyzed reaction has the catalyzer usage quantity trend (that is, can reduce the ratio of catalyzer usage quantity with respect to amount of substrate) of minimizing relatively if reaction scale increases.
And above-mentioned replacement(metathesis)reaction is from the viewpoint of reaction efficiency and output, and the another kind of alkene of the compound reaction of preferred use and following formula (77) carries out.At this moment alkene is not particularly limited, but from reaction efficiency, cost, viewpoint consideration such as operation easily, more preferably ethene for example.
When above-mentioned another kind of alkene for example was to use ethene, its operation and reaction principle were described as follows.That is, at first make the compound and the ethene chemical combination of following formula (77), make the bound fraction open loop of the alkene in the compound of following formula (77) by replacement(metathesis)reaction.Then, make this reaction product generation replacement(metathesis)reaction again and open loop, generate the compound of following formula (76) expression.Produce ethene once more by this ring-opening reaction, finally from reaction system, remove.Thus, can more effectively obtain the compound of following formula (76) expression.
Other use material and reaction conditions is not particularly limited in the above-mentioned replacement(metathesis)reaction, can be with reference to suitable selections such as existing replacement(metathesis)reactions.Solvent for example can use ether series solvents such as halogenide such as aromatic hydrocarbons such as toluene, dimethylbenzene or methylene dichloride, chloroform, ethylene dichloride or diethyl ether, glycol dimethyl ether, tetrahydrofuran (THF) or acetonitrile, the contour polar solvent of dimethyl sulfoxide (DMSO), and these solvents can use separately, also can two kinds or more kinds of being used in combination.Temperature of reaction and reaction times also are not particularly limited, can be according to the R in the following formula (77)
1～R
6, X
11, X
21And X
31Structure and suitable selection such as reaction scale.And the separation and the process for purification of reaction product also are not particularly limited, and can suit to use known method such as column chromatography and GPC to carry out.
As mentioned above, the compound by following formula (77) can prepare the compound of following formula (76).The preparation method of the compound of following formula (77) expression also is not particularly limited, but preferred package contains the compound of halogenation following formula (78)～(80) expression, again by inspiring confidence in now the preparation method that the coupling of (Wurtz) type makes the step of their cyclisation.
In formula (78)～(80), R
1～R
6, X
11, X
21And X
31Respectively with following formula (77) in identical.
Inspire confidence in type coupling now and be as the linked reaction between the halogenide and by known, the inventor finds that this reaction can be used for the compound of following formula (77).As the following formula halogen, can list for example fluorine, chlorine, bromine and iodine, this is more preferably bromine wherein.Reaction is for example carried out in the presence of basic metal such as sodium Metal 99.5, metallic lithium or catalyzer etc., and above-mentioned catalyzer can be enumerated for example copper catalyst, nickel catalyzator, palladium catalyst etc., and this is more preferably copper catalyst wherein.In addition, can under separate stage, prepare halogenide, and make its coupling, also can in reaction system, generate halogenide, and (not separation) makes its coupling in same reaction system.Among the present invention, above-mentionedly inspire confidence in type link coupled concrete operations now and reaction conditions is not particularly limited, for example can carry out as getting off.Promptly, at first prepare following formula (78)～(80) compound (following is called " diene ") and, tert.-butoxy potassium, n-Butyl Lithium hexane solution, 1,2-ethylene dibromide, cupric iodide (I) and solvent THF, these reactive material and solvent, reaction solvent are all wanted thorough drying.The usage quantity of the material beyond diene and the solvent is not particularly limited, but in order to suppress side reaction etc., more preferably all uses with identical chemical equivalent.Then, with the above-mentioned reactor of inert gas replacement, add t-BuOK and THF and make it dissolving.Then, temperature of reaction system is reduced to-78 ℃, adds diene, in 2 hours, drip the hexane solvent of n-Butyl Lithium again.After being added dropwise to complete, temperature of reaction system is warmed up to-40 ℃, restir 30 minutes.After then more above-mentioned system temperature being reduced to-78 ℃, adding glycol dibromide, and then be warmed up to-40 ℃, stirred one and a half hours.Then, more above-mentioned system temperature is rolled back-78 ℃ after, add cupric iodide (I).Then ,-78 ℃ down stir 4 hours after, stop cooling, Yi Bian slowly be returned to room temperature, Yi Bian restir 7 hours.According to the ordinary method operation, obtain the target compound of following formula (77) expression then.
Use material, temperature of reaction and the reaction times etc. in this reaction are not limited to top described, can inspire confidence in suitable selection such as type linked reaction now with reference to existing.And, in following formula (78)～(80), above-mentioned X
11～X
31In any one when being imino-, in order to suppress side reaction etc., more preferably its hydrogen atom replaces with protecting group.Be not particularly limited as protecting group; can suit to use known protecting group; for example can list the protecting group of record among " protecting group in the organic synthesis (the Protective Groups in Organic Synthesis) " the 2nd edition of Greene and Wuts work etc., tert-butoxycarbonyl (Boc), ethanoyl (Ac), benzyl oxidation carbonyl (Z), benzyl (Bz) etc. are specifically arranged.
In addition, the compound of following formula (77) is the cis body, but what obtain usually is mixture with the trans body of its isomer.They can use general methods such as GPC to separate.And then, as following formula X
11～X
31Incomplete when identical, can obtain the many by products beyond the target compound of following formula (77), but they can separate also by methods such as column chromatography and GPC.
In addition, the preparation method of the compound of following formula (77) is not limited to the above-mentioned type coupling method now that inspires confidence in, and can synthesize with known method.These known method for example have " Giuseppe Borsato, Ottorino De Lucchi, Fabrizio Fabris, Luca Groppo, Vittorio Lucchini, andAlfonso Zambon, J.Org.Chem., 2002,67, p.7894-7897." in the halogenide of record and the method for organometallic reagent cross-coupling and " Harold Hart, AbdollahBashir-Hashemi, Jihmei Luo and Mary Ann Meador, Tetrahedron, 1986,42, p.1641-1654.”，“Harold?Hart，Chung-yin?Lai，Godson?ChukuemekaNwokogu?and?Shamoui?Shamouilian，Tetrahedron，1987，43，p.5203-5224。" and " Francisco Raymo, Franz H.Kohnke and Francesca Cardullo, Tetrahedron, 1992,48, p.6827-6838. " etc. in the synthesis method etc. of record.But if use the above-mentioned type coupling method now that inspires confidence in, mode that also can be as previously described is such, after the compound halogenation with following formula (78)～(80) expression, in the reaction system identical with above-mentioned halogenation (not separating) carry out cyclisation.Like this, can 1 step just synthesize the compound of following formula (77) easily by the compound of following formula (78)～(80), thereby be preferred, at above-mentioned X
11～X
31All be effective especially under the situation of methylene radical.
Then, obtain the compound of following formula (77) after, according to aforesaid way, obtain the compound of following formula (76) by the replacement(metathesis)reaction of this compound.
In addition, the method as obtain the compound of following formula (76) from the compound of following formula (77) except above-mentioned replacement(metathesis)reaction, for example also can be obtained by following preparation method.That is, at first ozone decomposes the compound of following formula (77) expression, obtains the compound of following formula (77 ') expression.The condition that this ozone decomposes is not particularly limited, can be with reference to suitable selections such as known ozonolysis reactions.
In the formula, R
1～R
6Be respectively identical or different, be the alkyl or the aromatic hydrocarbyl of hydrogen atom, straight or branched, X
11, X
21And X
31Be respectively identical or different, be methylene radical, imino-or Sauerstoffatom, when it is under the situation of imino-, its hydrogen atom also can replace with protecting group.
Alleged ozone decomposes, and is as the compound ozonize that will have carbon carbon unsaturated link(age), and makes it further decompose reaction of obtaining carbonyl compound and by known.The ozone decomposition thing obtains the method for carbonyl compound, for example has by the method for water decomposition and the method for use reductive agent, more specifically, for example uses Zn-H in the presence of acetic acid
2The method of O epoxy, in the presence of platinum catalyst and palladium catalyst etc., use hydrogen contact the reductive method etc. of reductive method, use Raney nickel.Decomposing for ozone has many documents to be described, for example " P.S.Bailely, Chem.Rev., 1958,58, p.925. " and " R.W.Murray, Acc.Chem.Res., 1968,1, p.313. " etc.
In addition, the compound and the salt thereof of following formula (77 ') expression are new compounds of the present invention, preferably the preparation method who decomposes by the ozone that comprises the compound that following formula (77) is represented prepares, but also can use any method to prepare by being not limited to this preparation method.
Then, obtain the compound of following formula (77 ') expression after, obtain the compound of following formula (76) expression by its intramolecular linked reaction.The condition of this intramolecularly linked reaction is not particularly limited, can be with reference to suitable selections such as known reactions.Above-mentioned intramolecularly linked reaction is preferably used transition metal reductive linked reaction, and more preferably above-mentioned transition metal contains titanium.In addition, using the reductive coupling of the carbonyl compound of the titanium atom that hangs down the atom valence state is as the McMurry reaction and by known.The normal use for example reduced TiCl in reaction system
3Or TiCl
3(DME)
1.5Ligand (DME represents glycol dimethyl ether) produces the method for the titanium of above-mentioned low atom valence state, and reductive agent at this moment for example can use Zn (Cu) or C
8K (potassium graphite) etc.For McMurry reaction the document of many descriptions is arranged also, for example can list " J.E.McMurry, Acc.Chem.Res.; 1974,7, p.281. ", " J.E.McMurry; Acc.Chem.Res., 1983,16; p.405. ", " J.E.McMurry and K.L.Kees, J.Org.Chem., 1977; 42, p.2655. " and " D.L.J.Clive et al., J.Am.Chem.Soc.; 1988,110, p.6914. " etc.
After making the compound of above-mentioned chemical formula (76) expression as described above, its oxidation is prepared the compound of following formula (81) expression.
In the formula, R
1～R
6, X
11, X
21And X
31Respectively with following formula (76) in identical.
The condition of above-mentioned oxidizing reaction is not particularly limited, and can carry out under the condition identical with existing dehydrogenation reaction.For example, can use oxygenants such as DDQ and chloranil, but, preferably use catalyzer industrial.Above-mentioned catalyzer is not particularly limited, and can use normally used catalyzer in the dehydrogenation reaction, for example can use Pd-C (palladium carbon), platinum, rhodium, metal sulphur and metallic selenium etc.And these catalyzer can use separately, also can two or more be used in combination.
Other use material and reaction conditions also are not particularly limited, can be with reference to the setting by waiting with existing dehydrogenation reaction to suit.When using catalyzer such as oxygenants such as above-mentioned DDQ or Pd-C, reaction solvent can use for example aromatic hydrocarbons such as toluene, dimethylbenzene or ether series solvents such as dioxan, glycol dimethyl ether, these solvents can use separately, also can two kinds or more kinds of being used in combination.Temperature of reaction and reaction times are not particularly limited in this case, can be according to the suitable selections such as kind of reactive material.
Then, obtain the compound of following formula (81) expression after, replace X as required
11～X
31On hydrogen atom and R
1～R
6On benzyl position hydrogen atom, can obtain the compound of the present invention of following formula (1) expression.X
11～X
31In any one is an imino-, under the situation that its hydrogen atom replaces with protecting group, also can again it be replaced in case of necessity behind the imino-deprotection.The method of deprotection is not particularly limited, and can use known method aptly according to kind of above-mentioned protecting group etc.
Replace above-mentioned X
11～X
31On the method for hydrogen atom also be not particularly limited, can introduce various substituting groups by the method identical with the substitution reaction of the ditan with similar chemical structure, fluorenes and carbazole etc.X for example
11～X
31Any one when being methylene radical, in order to make this methylene radical alkylation, can use by butyllithium etc. and slough above-mentioned methylene radical, generate carbanion, add the method for iodate alkyl etc. again.In addition, in order to make its alkoxylate, use method usually, for example can use the method that makes its alcoholysis reaction after the halogenation etc. in the alkoxide of benzyl position.And then, at R
1～R
6On when having the hydrogen atom of benzyl position, the method that replaces its hydrogen atom also is not particularly limited, generally can and the substitution reaction of benzyl position carry out equally.For example, can when replacing, use with above-mentioned identical method etc. with alkyl or alkoxyl group.
As mentioned above, be not difficult to obtain the compound of the present invention of following formula (1) expression by the Synthetic Organic Chemistry method.But the preparation method of The compounds of this invention is not limited thereto, and also can prepare by any method.
The compound of the present invention of following formula (1) expression is applicable to the purposes such as raw material of electronic material, various fullerene and assorted fullerene.Particularly above-mentioned X
1～X
3One of any contain heteroatomic words, think that it is suitable as the synthesis material of assorted fullerene.
Moreover, have by the group of two or more a plurality of compound molecules derived from following formula (1) expression compound (following is called " crosslinked body ") by at least a structure that is connected of covalent linkage and cross linked chain, be also included within the compound of the present invention.Wherein, the structure of above-mentioned two or more a plurality of groups is identical or different each other.Above-mentioned cross linked chain is not particularly limited, and for example can be cross linked chain that contains alkylidene group, polyenoid, ester bond and ehter bond etc. etc.This wherein, for example be preferably alkylidene group, more preferably methylene radical or carbonatoms are 2～10 polymethylene, and, preferred above-mentioned two or more a plurality of group contain the carbon of at least one benzyl position separately, and with above-mentioned covalent linkage or cross linked chain bonded position on the carbon of above-mentioned benzyl position.
The manufacture method of crosslinked body so also is not particularly limited, and can use known method aptly according to structure of desired crosslinked body etc., is an example of this method below.That is, at first single halogenation is carried out in a position of the benzyl position of three cyclopenta triphenylenyl (compound of following formula (84)), make it and halogenated olefins for example 1, the 4-dibromobutane carries out linked reaction.This method is not particularly limited, for example have in single halogenide of above-mentioned three cyclopenta triphenylenyl the metal M of adding g make grignard reagent after, add 1 again, the 4-dibromobutane carries out the link coupled method.Like this, can obtain the compound that links to each other with tetramethylene between the benzyl position of three cyclopenta triphenylenyl.And then, as required, can obtain the crosslinked body of target by introducing substituting groups such as aforesaid methods in remaining benzyl position.
In addition, when in the compound of following formula (1) expression and crosslinked body thereof, having isomer such as tautomer, steric isomer, optical isomer, also comprise these isomer in the compound of the present invention.And then the compound of following formula (1) and other compound of the present invention also comprise this salt under can the salifiable situation of shape in the compound of the present invention.Above-mentioned salt is not particularly limited, and for example can be acid salt, base addition salt, and then the acid that forms above-mentioned acid salt can be mineral acid or organic acid, and the alkali that forms above-mentioned base addition salt can be mineral alkali or organic bases.Have no particular limits as above-mentioned mineral acid, can list for example sulfuric acid, phosphoric acid, hydrochloric acid, Hydrogen bromide and hydroiodic acid HI etc.Above-mentioned organic acid also is not particularly limited, and can list for example p-toluenesulphonic acids, methanesulfonic, oxalic acid, p-bromo-benzene sulfonic acid, carbonic acid, succsinic acid, citric acid, M-nitro benzoic acid and acetic acid etc.Be not particularly limited as above-mentioned mineral alkali, can list for example ammonium hydroxide, alkali metal hydroxide, alkaline earth metal hydroxides, carbonate and supercarbonate etc., more specifically, can list for example sodium hydroxide, potassium hydroxide, salt of wormwood, yellow soda ash, sodium bicarbonate, saleratus, calcium hydroxide and lime carbonate etc.Above-mentioned organic bases also is not particularly limited, and can list for example thanomin, triethylamine and three (methylol) aminomethane etc.
The preparation method of the salt of the invention described above compound also is not particularly limited, and for example can suit to add above-mentioned bronsted lowry acids and bases bronsted lowry in compound of the present invention, waits by known method to prepare.
In the following formula (1), A
1～A
6With above-mentioned X
1～X
3On substituting group preferably satisfy following condition.
(A
1～A
6With above-mentioned X
1～X
3On substituent condition)
A
1～A
6Be respectively identical or different, for the alkyl or the aromatic hydrocarbyl of hydrogen atom, straight or branched, at A
1～A
6On when having the hydrogen atom of benzyl position, its hydrogen atom can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different; be halogen; low molecule of a straight chain shape or a catenate or macromolecular chain (can contain heteroatoms in its main chain and the side chain; also can not contain heteroatoms; can contain unsaturated link(age); also can not contain unsaturated link(age); can contain ring texture; also can not contain ring texture); the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); saturated or unsaturated alkyl; hydroxyl; alkoxyl group; alkanoyloxy; amino; hydroxyl amino; alkylamino; dialkyl amido; alkyl amido; cyano group; nitro; sulfo group; the alkyl that replaces with one or more halogen atom; alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom); alkyl sulphonyl (its alkyl also can replace with one or more halogen atom); sulfamyl; alkylsulfamoyl group; carboxyl; formamyl; alkyl-carbamoyl; alkyloyl or alkoxy carbonyl perhaps are attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
Above-mentioned X
1～X
3On substituting group be same to each other or different to each other, as its bonded X
aWhen (a is any one integer of 1～3) is methylene radical or vinylidene base; this substituting group can be a halogen; low molecule of a straight chain shape or a catenate or macromolecular chain (can contain heteroatoms in its main chain and the side chain; also can not contain heteroatoms; can contain unsaturated link(age); also can not contain unsaturated link(age); can contain ring texture; also can not contain ring texture); the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); saturated or unsaturated alkyl; hydroxyl; alkoxyl group; alkanoyloxy; amino; hydroxyl amino; alkylamino; dialkyl amido; alkyl amido; cyano group; nitro; sulfo group; the alkyl that replaces with one or more halogen atom; alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom); alkyl sulphonyl (its alkyl also can replace with one or more halogen atom); sulfamyl; alkylsulfamoyl group; carboxyl; formamyl; alkyl-carbamoyl; alkanoyl or alkoxy carbonyl perhaps are attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
As its bonded X
aDuring for imino-methylene radical or imino-; this substituting group is a halogen; low molecule of a straight chain shape or a catenate or macromolecular chain (can contain heteroatoms in its main chain and the side chain; also can not contain heteroatoms; can contain unsaturated link(age); also can not contain unsaturated link(age); can contain ring texture; also can not contain ring texture); the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; can be saturated or undersaturated ring, can have substituting group; also can not have substituting group); saturated or unsaturated alkyl; hydroxyl; alkoxyl group; alkanoyloxy; the alkyl that replaces with one or more halogen atom; carboxyl; formamyl; alkyl-carbamoyl; alkyloyl or alkoxy carbonyl.
And, in the following formula (1), A
1～A
6With above-mentioned X
1～X
3On substituting group more preferably satisfy following condition.
(A
1～A
6With above-mentioned X
1～X
3On substituent condition)
A
1～A
6Be respectively identical or different, for hydrogen atom, carbonatoms are 1～6 straight or branched alkyl, phenyl or naphthyl, A
1～A
6On when having benzyl position hydrogen atom, its hydrogen atom also can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different; be halogen; be with or without the hydrocarbon chain of substituent saturated or undersaturated straight or branched; conjugated system macromolecular chain or oligomer chain; the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); hydroxyl; carbonatoms is 1～6 straight or branched alkyl; carbonatoms is 2～6 straight or branched unsaturated alkyl; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is 1～6 straight or branched alkyl; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is the alkyloyl of 1～6 straight or branched; or carbonatoms is the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
Above-mentioned X
1～X
3On substituting group be same to each other or different to each other,
As its bonded X
aWhen (a is any one integer of 1～3) is methylene radical or vinylidene base; this substituting group is a halogen; be with or without the hydrocarbon chain of substituent saturated or undersaturated straight or branched; conjugated system macromolecular chain or oligomer chain; the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
As its bonded X
aDuring for imino-methylene radical or imino-; this substituting group is a halogen; be with or without the hydrocarbon chain of substituent saturated or undersaturated straight or branched; conjugated system macromolecular chain or oligomer chain; the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; can be saturated or undersaturated ring, can have substituting group; also can not have substituting group); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched.
Then, in the following formula (1), A
1～A
6With above-mentioned X
1～X
3On substituting group more preferably satisfy following condition.
(A
1～A
6With above-mentioned X
1～X
3On substituent condition)
A
1～A
6Be respectively identical or different, for hydrogen atom, carbonatoms are 1～6 straight or branched alkyl, phenyl or naphthyl, A
1～A
6On when having benzyl position hydrogen atom, its hydrogen atom also can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different, be halogen, carbonatoms is 1～3000 (to be preferably 1～300 especially, most preferably be 1～30) straight chain shape alkyl (wherein, combination in the main chain can be respectively saturated bond or unsaturated link(age), hydrogen atom on the main chain can randomly replace with halogen atom or methyl), conjugated system macromolecular chain or oligomer chain, have any one hydrogen atom in the arbitrary compound that removes following formula (9)～(75) structure cyclic substituents (wherein, above-mentioned cyclic substituents also can further replace with one or more substituting groups, these substituting groups are same to each other or different to each other, and above-mentioned substituting group is a halogen atom, methyl, hydroxyl, methoxyl group, oxygen base or amino);
Hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
Above-mentioned X
1～X
3On substituting group be same to each other or different to each other,
As its bonded X
aWhen (a is any one integer of 1～3) is methylene radical or vinylidene base; this substituting group is a halogen; carbonatoms is 1～3000 (to be preferably 1～300 especially; most preferably be 1～30) straight chain shape alkyl (wherein the key in the main chain can be respectively saturated bond or unsaturated link(age); hydrogen atom on the main chain can randomly replace with halogen atom or methyl); conjugated system macromolecular chain or oligomer chain; have any one hydrogen atom in the arbitrary compound that removes aforementioned formula (9)～(75) structure cyclic substituents (wherein; above-mentioned cyclic substituents also can further replace with one or more substituting groups; these substituting groups are same to each other or different to each other; above-mentioned substituting group is a halogen atom; methyl; hydroxyl; methoxyl group; oxygen base or amino); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
As its bonded X
aDuring for imino-methylene radical or imino-; this substituting group is a halogen; carbonatoms is 1～3000 (to be preferably 1～300 especially; most preferably be 1～30) straight chain shape alkyl (wherein the key in the main chain can be respectively saturated bond or unsaturated link(age); hydrogen atom on the main chain can randomly replace with halogen atom or methyl); conjugated system macromolecular chain or oligomer chain; have any one hydrogen atom in the arbitrary compound that removes aforementioned formula (9)～(75) structure cyclic substituents (wherein; above-mentioned cyclic substituents also can further replace with one or more substituting groups; these substituting groups are same to each other or different to each other, and above-mentioned substituting group is a halogen atom; methyl; hydroxyl; methoxyl group; oxygen base or amino); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched.
In addition, " halogen " among the present invention refers to halogens arbitrarily, and fluorine, chlorine, bromine and iodine are for example arranged.And, as alkyl, be not particularly limited, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl etc., in its structure, contain in the group (for example alkoxyl group, alkylamino, alkoxy carbonyl etc.) of alkyl alkyl too.As unsaturated alkyl, be not particularly limited, can list for example vinyl, 1-propenyl, allyl group, propargyl, pseudoallyl, 1-butylene base and crotyl etc.As alkyloyl, be not particularly limited, can list for example formyl radical, ethanoyl, propionyl, isobutyryl, pentanoyl and isovaleryl etc., in its structure, contain in the group (alkanoyloxy, alkyl amido etc.) of alkyloyl alkyloyl too.And carbonatoms is that 1 alkyloyl is meant formyl radical, and the group that contains alkyloyl in its structure too.
Above-mentioned conjugated system macromolecular chain or oligomer chain more preferably are selected from polyhenylene, oligomeric penylene, polyphenylene vinylene, oligomeric penylene vinylene, polyenoid, oligomerisation of ethylene, polyacetylene, low polyacetylene, polypyrrole, low polypyrrole, Polythiophene, oligothiophene, polyaniline and Oligoaniline, and (they can replace with one or more substituting groups, can not replace yet) at least a, at this moment substituting group is preferably especially and is selected from least a in halogen atom, methyl, hydroxyl, methoxyl group, oxygen base and the amino.In addition, further preferred its formula weight of above-mentioned conjugated system macromolecular chain or oligomer chain is in 30～30000 scopes.Above-mentioned formula weight is preferably 50～5000 especially, most preferably is 50～1000.
In addition, in the following formula (1), be combined in above-mentioned same A
r(r is any one integer of 1～6) or same X
aSubstituting group on (a is any one integer of 1～3) is each other by covalent bonds, and with they bonded A of institute
rOr X
aForming carbocyclic ring or heterocycle together (can be monocycle or condensed ring, it can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) situation under, the atomicity that constitutes above-mentioned ring is 3～20, and above-mentioned substituting group is preferably and is selected from least a in halogen atom, methyl, hydroxyl, methoxyl group, oxygen base and the amino.
In addition, in the following formula (1), if above-mentioned X
1～X
3On substituting group at least one, with its bonded X
aFurther with this X
aInstitute's bonded phenyl ring becomes one and forms conjugated system, can more preferably be applicable to purposes such as electronic material.Such compound exists in a large number, and the compound of following formula (89)～(91) expression is for example arranged.The compound of formula (89)～(91) only is to be used for being not limited to this for example.
In the following formula (1), above-mentioned X
1～X
3On substituting group not exist (be above-mentioned X
1～X
3On any one of hydrogen atom all need not be above-mentioned substituting group replace) compound, can be used for the synthesis material of other derivative for example etc.
Work as A
1～A
6When all being hydrogen atom, be suitable for synthesis material etc. sometimes, thereby be preferred, A
1～A
6When containing alkyl or aromatic hydrocarbyl, be preferred for synthesizing of corresponding derivative etc.
And, in above-mentioned (1), X
1～X
3Be preferably and for example be selected from least a in methylene radical, vinylidene base, imino-and the Sauerstoffatom, more preferably X
1～X
3It all is methylene radical.Especially, A
1～A
6All be hydrogen atom, and X
1～X
3All be methylene radical, its any one all do not have substituted compound, promptly three cyclopenta triphenylenyl of parent compound wait as the synthesis material of various derivatives easily and use.
And then ligand of the present invention is the ligand of the chelation structure of the The compounds of this invention that contains following formula (1) expression or its crosslinked body and metallic element, and the compound of following formula (1) or its crosslinked body also can be its tautomer or steric isomer.Ligand of the present invention or its salt can be preferred for for example field such as photosensitizers, catalyzer, but their purposes without limits.Polymerizing catalyst more preferably when being used for catalyzer.Above-mentioned metallic element can contain single metallic element, also can contain or two kinds or more kinds of metallic element, preferably contain transition metal, this transition metal more preferably contains at least a metal that is selected from yttrium (Y), samarium (Sm), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), iridium (Ir), cobalt (Co), rhodium (Rh), tungsten (W), nickel (Ni), palladium (Pd), platinum (Pt) and the osmium (Os).
Photosensitizers of the present invention closes catalyzer by containing the invention described above ligand or its salt, and electronic material of the present invention all demonstrates excellent performance respectively by containing compound of the present invention, its tautomer or steric isomer or their salt.
(embodiment)
Then, embodiments of the invention are described.
(condition determination etc.)
Nucleus magnetic resonance (NMR) spectrum be to use the instrument that is called Mercury300 (trade(brand)name) that Varian company makes (
1300MHz when H measures) measures.Chemical shift is represented with 1,000,000/(ppm).When being to use tetramethylsilane (TMS), internal standard 0ppm obtains.Coupling constant (J) represents that with Hz shorthand notation s, d, t, q, m and br represent unimodal (singlet), bimodal (doublet), three peaks (triplet), four peaks (quartet), multimodal (multiplet) and broad peak (broad) respectively.High resolution mass spectrometry (HRMS) is to use JMS-DX-303 (trade(brand)name) that JEOL company makes, measures according to electron bombardment method or chemical ion method.The U-3500 (trade(brand)name) that ultraviolet-visible absorption spectroscopy and emmission spectrum (UV-VIS) are to use Hitachi company limited to make measures.Measured value (wavelength) is represented with nm.Infrared absorption spectrum (IR) be to use the manufacturing of Japan branchs Optical Co., Ltd FT/IR 480plus (trade(brand)name), measure according to the KBr method.Measured value (wave number) is used cm
-1Represent, shorthand notation m and w represent respectively medium and a little less than.Fusing point be to use this making of willow the YanagimotoMicroPointApparatus (trade(brand)name) that makes of limited corporate system measure.The column chromatography separation is to use silica gel (commodity Wakogel CF-200 by name and the pure pharmaceutical worker's industry of light company limited).The flat board that thin-layer chromatography (TLC) uses is to use the Wakogel BF-5 (trade(brand)name) that makes with the pure pharmaceutical worker's industry of light company limited.The LC-908 (trade(brand)name) that GPC is to use Japanese analytical industry company limited to make carries out.All chemical substances all are pharmaceutical grade.Norbornadiene is to change into Industrial Co., Ltd to buy (500mL, 16000 yen) from Tokyo.The hexane solution of n-Butyl Lithium is to buy (PCy from Northeast chemistry company limited
3)
2RuCl
2=CHPh buys from Aldrich company, and ethene is to buy from Osaka oxygen Industrial Co., Ltd, and t-BuOK, glycol dibromide, cupric iodide (I), toluene and DDQ are from buying with the pure pharmaceutical worker's industry of light company limited.
(synthesizing of three cyclopenta triphenylenyl)
Come synthesizing tricyclic pentadiene and triphenylenyl according to aforesaid equation 1.List above-mentioned equation 1 below once more.
Reaction conditions
D) BuLi, t-BuOK, BrCH
2CH
2Br, THF ,-78 ℃～-45 ℃ next CuI, room temperatures
E) (the PCy of catalytic amount
3)
2RuCl
2=CHPh, CH
2=CH
2, toluene, 0 ℃～80 ℃
F) DDQ, toluene, 110 ℃
The following describes concrete operation and sequential scheduling.
[step a: suitable-benzo three (norbornadiene) following formula (87) synthetic]
At first, use argon replaces after the three-necked bottle vacuum and heating drying to 1L, (120mmol 13.5g) and dehydration THF, stirs to add the t-BuOK of 180mL therein.Then, after the temperature of reaction system is reduced to-78 ℃, the compound norbornadiene (2 that adds following formula (86) expression while stirring, the 5-norbornadiene, 240mmol, 22.1g), then in 2 hours, drip the hexane solution (concentration 1.56mol/L is equivalent to the n-Butyl Lithium of 120mmol) of n-Butyl Lithium.After dripping, reaction system is warmed up to-40 ℃, restir 30 minutes.After then more above-mentioned system temperature being reduced to-78 ℃, (60mmol 11.3g), and then is warmed up to-40 ℃, stirs one and a half hours to add glycol dibromide.Then, more above-mentioned system temperature is reduced to-78 ℃ after, add cupric iodide (I) (120mmol, 22.9g).Then, after stirring 4 hours under-78 ℃, stop cooling, the limit makes it slowly be returned to the continuation of room temperature limit and stirred 7 hours.Use saturated aqueous ammonium chloride solution stopped reaction then, carry out C salt and filter.Extract this filtrate with ether, and then after fully extracting residual water layer with ether, water cleans the organic layer that merges, and uses MgSO
4Dry.Then, under reduced pressure heat up in a steamer desolvate after, with silica gel column chromatography (hexane: methylene dichloride=4: 1) separate residue, obtain the diastereoisomer mixture of suitable-benzo three (norbornadiene) (syn-benzotris (nobornadiene)) and anti--benzo three (norbornadiene) (anti-benzotris (nobornadiene)).And then, separate this mixture by GPC, obtain target product suitable-benzo three (norbornadiene) (output 108mg, isolated yield 2%) and anti--benzo three (norbornadiene) (output 270mg, isolated yield 5%).The physics value of representing this compound below.
Suitable-benzo three (norbornadiene): HRMS:270,1403, fusing point: 195 ℃ (dec),
1H-NMR (300MHz, CDCl
3): δ=6.57 (t, J=1.8Hz, 6H), 3.90-3.87 (m, 6H), 2.22 (dt, J=7.2,1.5Hz, 3H), 2.08 (dt, J=7.2,1.5Hz, 3H);
13C-NMR (75MHz, CDCl
3): 141.59,137.66,66.73,17.44ppm.
Instead-benzo three (norbornadiene):
1H-NMR (300MHz, CDCl
3): δ=6.68 (t, J=1.8Hz, 2H), 6.65 (dd, J=5.4,3.0Hz, 2H), 6.59 (dd, J=5.4,3.0Hz, 2H), 3.90-3.87 (m, 2H), 3.87-3.85 (m, 4H), 2.05 (dt, J=7.2,1.5Hz, 4H), 2.00 (dt, J=7.2,1.5Hz, 4H)
[step b: six hydrogen, three cyclopenta triphenylenyl (following formula (88)) synthetic]
At first, use argon replaces after the three-necked bottle vacuum and heating drying to 200mL, add suitable-benzo three (norbornadiene) (0.074mmol, solution 20mg) that is dissolved in 100mL toluene therein.Then, system temperature is reduced to-78 ℃, bubbling and fully introduce ethylene gas makes in the above-mentioned system to remain in the ethene atmosphere.Then, the temperature retrieval with above-mentioned system arrives room temperature, adding (PCy
3)
2RuCl
2(0.0037mmol, 3mg 5mol%), are keeping ethene atmosphere and were at room temperature stirring 24 hours=CHPh.Then, make in the above-mentioned system to remain under the argon gas atmosphere, reflux was used the filtered through silica gel reaction mixture after 48 hours.Under reduced pressure heat up in a steamer the solvent of this filtrate, by tlc (hexane: toluene=5: 1) separate the thick product that obtains, finally refining by GPC, obtain target compound six hydrogen, three cyclopenta triphenylenyl (hexahydrosumanene) (output 4mg, isolated yield 20%).The physics value of below representing this compound.
HRMS: Found: m/z=270.1412, the C of calculating
21H
18: M=270.1408, fusing point: 180 ℃ (dec),
1H-NMR (300MHz, CDCl
3): δ=5.69 (s, 6H), 3.90-3.87 (m, 6H), 3.81 (dd, 6H, J=9.9 and 7.2Hz), 2.78 (dt, 3H, J=11.4 and 7.2Hz), 1.01 (dt, 3H, J=9.9 and 11.4Hz);
13C-NMR (75MHz, CDCl
3): 141.91,129.28,43.66,40.35ppm.; IR (KBr): ν=3010 (m), 2919 (m), 2814 (m), 1595 (m), 1445 (m), 1260 (m) cm
-1UV-VIS (CH
2Cl
2): maximum absorption wavelength (Absorption λ max)=240nm, maximum emission wavelength (Emission λ max)=331nm (excitation wavelength (Excitation λ=240nm)
[step c: three cyclopenta triphenylenyl (following formula (84)) synthetic]
At first, use argon replaces after the two neck bottle vacuum and heating dryings to 10mL.Then, therein with syringe add six hydrogen, the three cyclopenta triphenylenyl be dissolved in 2mL toluene (0.011mmol, solution 3mg), and then add DDQ (0.0385mmol, 9mg) after, 110 ℃ of heating 20 hours down.After reaction is finished, under reduced pressure heat up in a steamer and desolvate, separate residue, obtain target compound three cyclopenta triphenylenyl (output 2mg, separation yield 67%) by tlc (hexane).The physics value of representing this compound below.And, the UV-VIS abosrption spectrogram of this compound of expression in Fig. 1～5.The use solvent is, Fig. 1 is hexahydroaniline (CHA), and Fig. 2 is tetrahydrofuran (THF) (THF), and Fig. 3 is acetonitrile (CH
3CN), Fig. 4 is methylene dichloride (CH
2Cl
2), strength of solution all is 1.0 * 10
-4M.And Fig. 5 is the spectrogram that Fig. 1～4 are all gathered.
HRMS: Found: m/z=264.0923, the C of calculating
21H
12: M=264.0939, fusing point: 115 ℃ (dec),
1H-NMR (300MHz, CDCl
3): δ=7.01 (s, 6H), 4.71 (d, J=19.5Hz, 3H), 3.42 (d, J=19.5Hz, 3H);
13C-NMR (75MHz, CDCl
3): 148.78,148.60,123.15,41.77ppm.; IR (KBr): ν=2950 (m), 2922 (m), 1653 (m), 1558 (m) cm
-1UV-VIS (hexahydroaniline (CHA), 1.0 * 10
-4M): maximum absorption wavelength (Absorption λ max)=276nm (log ε=4.25), UV-VIS (CH
2Cl
2): maximum absorption wavelength (Absorption λ max)=278nm, maximum emission wavelength (Emission λ max)=376nm (excitation wavelength (Excitation λ=278nm)
In addition, measure variable temperatures from 25 ℃ to 140 ℃
1H-NMR (300MHz, d
10-p-dimethylbenzene), as a result critical temperature Tc 140 ℃ or more than, counter-rotating can Δ G
*Calculate according to above-mentioned Tc and chemical displacement value, coupling constant J, 19.4kcal/mol or more than.
As mentioned above, manufacturing method according to the invention, can from cheaply and the norbornadiene that obtains easily begin only with 3 step synthesizing tricyclic pentadienes and triphenylenyl.And the reaction conditions of Overall Steps all relaxes very much, for example by using dehydrogenation catalyst to replace DDQ etc., commercial run is oversimplified, so that a large amount of synthetic.
By above-mentioned explanation,, can provide three cyclopenta triphenylenyl and derivative thereof, their preparation method according to the present invention.Preparation in accordance with the present invention, can be under the demulcent condition a large amount of synthesizing tricyclic pentadienes and triphenylenyl.And,, can also synthesize and be difficult to the fullerene and unknown fullerene, the assorted fullerene etc. that obtain at present as synthesis material with three cyclopenta triphenylenyl of the present invention and derivative thereof, the design that can be expected for novel material opens up new prospect.And then compound of the present invention not only is worth high as synthesis material, and himself also has very big value as the fundamental researchs such as model compound of bag type fullerene compound in industrial material such as electronic material and the metal with material.That is, compound of the present invention can obtain widespread use in the field of electronic materials of expectation fullerene and carbon nanotube application at present, expects that simultaneously it is all obtaining to use widely aspect basic technology and the utilisation technology two.And then, for example expect also by making complexings such as The compounds of this invention and transition metal, thereby obtain to use that the utility value on its industry is very big in fields such as photosensitizers and polymerizing catalysts.
Claims (40)
1, a kind of compound, its tautomer or steric isomer or their salt by following general formula (1) expression,
In the formula, A
1～A
6Be respectively identical or different, for hydrogen atom, straight or branched alkyl or aromatic hydrocarbyl, at A
1～A
6On when having the hydrogen atom of benzyl position, its hydrogen atom can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different, for halogen, straight chain shape or the low molecule of a catenate or macromolecular chain (can contain heteroatoms, also can not contain heteroatoms in its main chain and the side chain, unsaturated link(age) can be contained, also unsaturated link(age) can be do not contained, can contain ring texture, also can not contain ring texture), (it can be monocycle or condensed ring for carbocyclic ring or heterocycle, it can be saturated or undersaturated ring, can have substituting group, also can not have substituting group), electron-donating group or electron-withdrawing group, perhaps be attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
X
1～X
3Be respectively identical or different, be methylene radical (following formula (2)), vinylidene base (following formula (3)), carbonyl (following formula (4)), thiocarbonyl (following formula (5)), imino-methylene radical (following formula (6)), imino-(following formula (7)) or Sauerstoffatom (following formula (8)), X
1～X
3On when having hydrogen atom, its hydrogen atom also can replace with substituting group,
Above-mentioned X
1～X
3On substituting group be respectively identical or different, for halogen, straight chain shape or the low molecule of a catenate or macromolecular chain (can contain heteroatoms, also can not contain heteroatoms in its main chain and the side chain, unsaturated link(age) can be contained, also unsaturated link(age) can be do not contained, can contain ring texture, also can not contain ring texture), (it can be monocycle or condensed ring for carbocyclic ring or heterocycle, it can be saturated or undersaturated ring, can have substituting group, also can not have substituting group), electron-donating group or electron-withdrawing group, perhaps be attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together.
2, according to compound, its tautomer or steric isomer or their salt of claim 1 record, wherein in the following formula (1), A
1～A
6With above-mentioned X
1～X
3On substituting group satisfy following condition:
(A
1～A
6With above-mentioned X
1～X
3On substituent condition)
A
1～A
6Be respectively identical or different, for the alkyl or the aromatic hydrocarbyl of hydrogen atom, straight or branched, at A
1～A
6On when having the hydrogen atom of benzyl position, its hydrogen atom can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different; be halogen; low molecule of a straight chain shape or a catenate or macromolecular chain (can contain heteroatoms in its main chain and the side chain; also can not contain heteroatoms; can contain unsaturated link(age); also can not contain unsaturated link(age); can contain ring texture; also can not contain ring texture); the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); saturated or unsaturated alkyl; hydroxyl; alkoxyl group; alkanoyloxy; amino; hydroxyl amino; alkylamino; dialkyl amido; alkyl amido; cyano group; nitro; sulfo group; the alkyl that replaces with one or more halogen atom; alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom); alkyl sulphonyl (its alkyl also can replace with one or more halogen atom); sulfamyl; alkylsulfamoyl group; carboxyl; formamyl; alkyl-carbamoyl; alkyloyl or alkoxy carbonyl perhaps are attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
Above-mentioned X
1～X
3On substituting group be same to each other or different to each other, as its bonded X
aWhen (a is any one integer of 1～3) is methylene radical or vinylidene base; this substituting group can be a halogen; low molecule of a straight chain shape or a catenate or macromolecular chain (can contain heteroatoms in its main chain and the side chain; also can not contain heteroatoms; can contain unsaturated link(age); also can not contain unsaturated link(age); can contain ring texture; also can not contain ring texture); the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); saturated or unsaturated alkyl; hydroxyl; alkoxyl group; alkanoyloxy; amino; hydroxyl amino; alkylamino; dialkyl amido; alkyl amido; cyano group; nitro; sulfo group; the alkyl that replaces with one or more halogen atom; alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom); alkyl sulphonyl (its alkyl also can replace with one or more halogen atom); sulfamyl; alkylsulfamoyl group; carboxyl; formamyl; alkyl-carbamoyl; alkyloyl or alkoxy carbonyl perhaps are attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
As its bonded X
aDuring for imino-methylene radical or imino-; this substituting group is a halogen; low molecule of a straight chain shape or a catenate or macromolecular chain (can contain heteroatoms in its main chain and the side chain; also can not contain heteroatoms; can contain unsaturated link(age); also can not contain unsaturated link(age); can contain ring texture; also can not contain ring texture); the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; can be saturated or undersaturated ring, can have substituting group; also can not have substituting group); saturated or unsaturated alkyl; hydroxyl; alkoxyl group; alkanoyloxy; the alkyl that replaces with one or more halogen atom; carboxyl; formamyl; alkyl-carbamoyl; alkyloyl or alkoxy carbonyl.
3, according to compound, its tautomer or steric isomer or their salt of claim 1 record, wherein in the following formula (1), A
1～A
6With above-mentioned X
1～X
3On substituting group satisfy following condition:
(A
1～A
6With above-mentioned X
1～X
3On substituent condition)
A
1～A
6Be respectively identical or different, for hydrogen atom, carbonatoms are 1～6 straight or branched alkyl, phenyl or naphthyl, A
1～A
6On when having benzyl position hydrogen atom, its hydrogen atom also can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different; be halogen; be with or without the hydrocarbon chain of substituent saturated or undersaturated straight or branched; conjugated system macromolecular chain or oligomer chain; the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); hydroxyl; carbonatoms is 1～6 straight or branched alkyl; carbonatoms is 2～6 straight or branched unsaturated alkyl; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is 1～6 straight or branched alkyl; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is the alkyloyl of 1～6 straight or branched; or carbonatoms is the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
Above-mentioned X
1～X
3On substituting group be same to each other or different to each other,
As its bonded X
aWhen (a is any one integer of 1～3) is methylene radical or vinylidene base; this substituting group is a halogen; be with or without the hydrocarbon chain of substituent saturated or undersaturated straight or branched; conjugated system macromolecular chain or oligomer chain; the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; it can be saturated or undersaturated ring; can have substituting group; also can not have substituting group); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
As its bonded X
aDuring for imino-methylene radical or imino-; this substituting group is a halogen; be with or without the hydrocarbon chain of substituent saturated or undersaturated straight or branched; conjugated system macromolecular chain or oligomer chain; the atomicity that constitutes ring is that (it can be monocycle or condensed ring for 3～20 carbocyclic ring or heterocycle; can be saturated or undersaturated ring, can have substituting group; also can not have substituting group); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched.
4, according to compound, its tautomer or steric isomer or their salt of claim 1 record, wherein in the following formula (1), A
1～A
6With above-mentioned X
1～X
3On substituting group satisfy following condition:
(A
1～A
6With above-mentioned X
1～X
3On substituent condition)
A
1～A
6Be respectively identical or different, for hydrogen atom, carbonatoms are 1～6 straight or branched alkyl, phenyl or naphthyl, A
1～A
6On when having the hydrogen atom of benzyl position, its hydrogen atom also can replace with substituting group,
Above-mentioned A
1～A
6On substituting group be respectively identical or different, be halogen, carbonatoms be 1～3000 straight chain shape alkyl (wherein, combination in the main chain can be respectively saturated bond or unsaturated link(age), hydrogen atom on the main chain can randomly replace with halogen atom or methyl), conjugated system macromolecular chain or oligomer chain, have any one hydrogen atom in the arbitrary compound that removes following formula (9)～(75) structure cyclic substituents (wherein, above-mentioned cyclic substituents also can further replace with one or more substituting groups, these substituting groups are same to each other or different to each other, and above-mentioned substituting group is a halogen atom, methyl, hydroxyl, methoxyl group, oxygen base or amino);
Hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same A
rSubstituting group on (r is any one integer of 1～6) also can pass through covalent bonds each other, and with they bonded A of institute
rForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
Above-mentioned X
1～X
3On substituting group be same to each other or different to each other,
As its bonded X
aWhen (a is any one integer of 1～3) is methylene radical or vinylidene base; this substituting group is a halogen; carbonatoms is that (wherein the key in the main chain can be respectively saturated bond or unsaturated link(age) for 1～3000 straight chain shape alkyl; hydrogen atom on the main chain can randomly replace with halogen atom or methyl); conjugated system macromolecular chain or oligomer chain; have any one hydrogen atom in the arbitrary compound that removes aforementioned formula (9)～(75) structure cyclic substituents (wherein; above-mentioned cyclic substituents also can further replace with one or more substituting groups; these substituting groups are same to each other or different to each other; above-mentioned substituting group is a halogen atom; methyl; hydroxyl; methoxyl group; oxygen base or amino); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; amino; hydroxyl amino; carbonatoms is the alkylamino of 1～6 straight or branched; dialkyl amido (its alkyl is that carbonatoms is the alkyl of 1～6 straight or branched); carbonatoms is the alkyl amido of 1～6 straight or branched; cyano group; nitro; sulfo group; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carbonatoms is the alkoxyl group alkylsulfonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; carbonatoms is the alkyl sulphonyl (its alkyl also can replace with one or more halogen atom) of 1～6 straight or branched; sulfamyl; carbonatoms is the alkylsulfamoyl group of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched, perhaps is attached to same X
aSubstituting group on (a is any one integer of 1～3) also can pass through covalent bonds each other, and with they bonded X of institute
aForm carbocyclic ring or heterocycle (can be monocycle or condensed ring, can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) together,
As its bonded X
aDuring for imino-methylene radical or imino-; this substituting group is a halogen; carbonatoms is that (wherein the key in the main chain can be respectively saturated bond or unsaturated link(age) for 1～3000 straight chain shape alkyl; hydrogen atom on the main chain can randomly replace with halogen atom or methyl); conjugated system macromolecular chain or oligomer chain; have any one hydrogen atom in the arbitrary compound that removes aforementioned formula (9)～(75) structure cyclic substituents (wherein; above-mentioned cyclic substituents also can further replace with one or more substituting groups; these substituting groups are same to each other or different to each other, and above-mentioned substituting group is a halogen atom; methyl; hydroxyl; methoxyl group; oxygen base or amino); hydroxyl; carbonatoms is the alkyl of 1～6 straight or branched; carbonatoms is the unsaturated alkyl of 2～6 straight or branched; carbonatoms is the alkoxyl group of 1～6 straight or branched; carbonatoms is the alkanoyloxy of 1～6 straight or branched; the carbonatoms that replaces with one or more halogen atom is the alkyl of 1～6 straight or branched; carboxyl; formamyl; carbonatoms is the alkyl-carbamoyl of 1～6 straight or branched; carbonatoms is that the alkyloyl of 1～6 straight or branched or carbonatoms are the alkoxy carbonyl of 1～6 straight or branched.
5, according to claim 3 or 4 compound, its tautomer or steric isomer or their salt of putting down in writing, wherein above-mentioned conjugated system macromolecular chain or oligomer chain are selected from least a of polyhenylene, oligomeric penylene, polyphenylene vinylene, oligomeric penylene vinylene, polyenoid, oligomerisation of ethylene, polyacetylene, low polyacetylene, polypyrrole, low polypyrrole, Polythiophene, oligothiophene, polyaniline and Oligoaniline (they can replace with more than one substituting group, also can not replace).
6, according to compound, its tautomer or steric isomer or their salt of claim 5 record, wherein above-mentioned substituting group is selected from least a of halogen atom, methyl, hydroxyl, methoxyl group, oxygen base and amino.
7, according to compound, its tautomer or steric isomer or their salt of claim 3 or 4 records, the formula weight of wherein above-mentioned conjugated system macromolecular chain or oligomer chain is in 30～30000 scope.
8, according to compound, its tautomer or steric isomer or their salt of claim 1 record, in the wherein above-mentioned formula (1), be combined in above-mentioned same A
r(r is any one integer of 1～6) or same X
aSubstituting group on (a is any one integer of 1～3) is mutually with covalent bonds, and with they bonded A of institute
rOr X
aForming carbocyclic ring or heterocycle together (can be monocycle or condensed ring, it can be saturated or undersaturated ring, can have substituting group, also can not have substituting group) situation under, the atomicity that constitutes above-mentioned ring is 3～20, and above-mentioned substituting group is be selected from halogen atom, methyl, hydroxyl, methoxyl group, oxygen base and amino at least a.
9, compound, its tautomer or steric isomer or their salt of putting down in writing according to claim 1, in the wherein above-mentioned formula (1), above-mentioned X
1～X
3On substituting group at least one and its bonded X
aAnd further with this X
aInstitute's bonded phenyl ring becomes one and forms conjugated system.
10, compound, its tautomer or steric isomer or their salt of putting down in writing according to claim 1, in the wherein above-mentioned formula (1), A
1～A
6It all is hydrogen atom.
11, compound, its tautomer or steric isomer or their salt of putting down in writing according to claim 1, in the wherein above-mentioned formula (1), above-mentioned X
1～X
3On do not have substituting group (that is above-mentioned X,
1～X
3On any one of hydrogen atom above-mentioned substituting group all of no use replace).
12, compound, its tautomer or steric isomer or their salt of putting down in writing according to claim 1, in the wherein above-mentioned formula (1), X
1～X
3For being selected from least a in methylene radical, vinylidene base, imino-and the Sauerstoffatom.
13, compound, its tautomer or steric isomer or their salt of putting down in writing according to claim 1, in the wherein above-mentioned formula (1), X
1～X
3It all is methylene radical.
14, a kind of have by two or more derived from the group of the compound molecule of the claim 1 record compound by at least a structure that is connected of covalent linkage and cross linked chain, its tautomer or steric isomer or their salt, wherein above-mentioned two or more unit structures are same to each other or different to each other.
15, the compound of putting down in writing according to claim 14, its tautomer or steric isomer or their salt, wherein above-mentioned cross linked chain is that methylene radical or carbonatoms are 2～10 polymethylene, and above-mentioned plural group contains the carbon of at least one benzyl position respectively, and and above-mentioned covalent linkage or cross linked chain bonded position on the carbon of above-mentioned benzyl position.
16, a kind of ligand or its salt that contains the chelation structure of claim 1 or 14 compounds of putting down in writing or its tautomer or steric isomer and metallic element formation.
17, according to ligand or its salt of claim 16 record, wherein above-mentioned metallic element comprises transition metal.
18, according to ligand or its salt of claim 17 record, wherein above-mentioned transition metal contains at least a metal that is selected from yttrium (Y), samarium (Sm), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), iridium (Ir), cobalt (Co), rhodium (Rh), tungsten (W), nickel (Ni), palladium (Pd), platinum (Pt) and the osmium (Os).
19, the compound or its salt of following formula (76) expression,
In the formula, R
1～R
6Be identical or different each other, be the alkyl or the aromatic hydrocarbyl of hydrogen atom, straight or branched, X
11, X
21And X
31Be methylene radical, imino-or Sauerstoffatom, when it was imino-, its hydrogen atom also can replace with protecting group with being same to each other or different to each other.
20, the compound or its salt of putting down in writing according to claim 19, wherein R
1～R
6Being identical or different each other, is alkyl, the phenyl or naphthyl of 1～6 straight or branched for hydrogen atom, carbonatoms.
21, according to the manufacture method of the compound or its salt of claim 19 record, comprising the replacement(metathesis)reaction of the compound of following formula (77) expression,
In the formula, R
1～R
6, X
11, X
21And X
31Identical with following formula (76) respectively.
22, according to the preparation method of claim 21 record, wherein above-mentioned replacement(metathesis)reaction uses catalyzer to carry out.
23, according to the preparation method of claim 22 record, wherein above-mentioned catalyzer contains at least a element that is selected from ruthenium, aluminium, titanium, molybdenum and the tungsten.
24, according to the preparation method of claim 22 record, wherein above-mentioned catalyzer contains and is selected from (PCy
3)
2RuCl
2=CHPh, Al (C
2H
5)
3-TiCl
4, Al (C
2H
5)
3-MoCl
3And Al (C
2H
5)
3-WCl
6At least a.
25, according to the preparation method of claim 21 record, the another kind of alkene of the compound reaction of wherein above-mentioned replacement(metathesis)reaction use and following formula (77) carries out.
26, according to the preparation method of claim 25 record, wherein above-mentioned alkene is ethene.
27, the compound or its salt of following formula (77 ') expression,
In the formula, R
1～R
6Be identical or different each other, be the alkyl or the aromatic hydrocarbyl of hydrogen atom, straight or branched, X
11, X
21And X
31Be methylene radical, imino-or Sauerstoffatom, when it was imino-, its hydrogen atom also can replace with protecting group with being same to each other or different to each other.
28, according to the preparation method of the compound or its salt of claim 27 record, decompose comprising the ozone of the compound of following formula (77) expression, wherein, the compound of following formula (77) expression is the compound of record in the claim 21.
29, according to the preparation method of the compound or its salt of claim 19 record, it comprises the intramolecularly linked reaction of the compound of claim 27 record.
30, according to the preparation method of claim 29 record, wherein above-mentioned intramolecularly linked reaction is for using transition metal reductive linked reaction.
31, according to the preparation method of claim 30 record, wherein above-mentioned transition metal comprises titanium.
32, the preparation method of the compound of following formula (77) expression, it comprises the compound halogenation with following formula (78)～(80) expression, again by inspiring confidence in the step that type coupling now makes their cyclisation, wherein, the compound of following formula (77) expression is the compound of record in the claim 21
In formula (78)～(80), R
1～R
6, X
11, X
21And X
31Respectively with following formula (77) in identical.
33,, wherein carry out the above-mentioned type link coupled cyclisation now that inspires confidence in the presence of at least a in being selected from basic metal, copper catalyst, nickel catalyzator and palladium catalyst according to the preparation method of claim 32 record.
34, according to the preparation method of claim 32 record, it carries out the cyclisation of above-mentioned Wei Erci type link coupled in the reaction system identical with above-mentioned halogenation behind the compound of halogenation following formula (78)～(80) expression.
35, the preparation method who puts down in writing according to claim 32, it carries out the halogenation and the cyclisation of Wei Erci type link coupled of the compound of following formula (78)～(80) expression by using tert.-butoxy potassium, n-Butyl Lithium hexane solution, glycol dibromide, cupric iodide (I) and tetrahydrofuran (THF).
36,, prepare the step of the compound of following formula (77) expression comprising preparation method by claim 32 record according to the preparation method of claim 21 or 29 records.
37, compound, its tautomer or steric isomer or their salt of claim 1 or 14 records, perhaps according to the ligand of claim 16 record or the preparation method of its salt, the step for preparing the compound of following formula (81) expression comprising the compound of oxidation claim 19 record
In the formula, R
1～R
6, X
11, X
21And X
31Respectively with following formula (76) in identical.
38, comprise claim 1 or compound, its tautomer or the steric isomer of 14 records or the electronic material of their salt.
39, comprise the ligand of claim 16 record or the photosensitizers of its salt.
40, comprise the ligand of claim 16 record or the catalyzer of its salt.
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|---|---|---|---|
| JP2003024462 | 2003-01-31 | ||
| JP024462/2003 | 2003-01-31 |
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|---|---|
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ID=32820767
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|---|---|---|---|
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| Country | Link |
|---|---|
| US (1) | US7435859B2 (en) |
| EP (1) | EP1604949A2 (en) |
| JP (1) | JP4716868B2 (en) |
| KR (1) | KR20050097531A (en) |
| CN (1) | CN1745050A (en) |
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|---|---|---|---|---|
| CN114805376A (en) * | 2022-04-15 | 2022-07-29 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and organic electroluminescent device comprising same |
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| JP4883955B2 (en) * | 2004-07-30 | 2012-02-22 | 国立大学法人大阪大学 | Organic semiconductor and electronic device using the same |
| JP2009046392A (en) * | 2005-12-05 | 2009-03-05 | National Institutes Of Natural Sciences | Triazasumanene compounds, and method for producing the same |
| US11917843B2 (en) | 2017-07-26 | 2024-02-27 | Universal Display Corporation | Organic electroluminescent materials and devices |
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-
2004
- 2004-01-27 CN CNA2004800032191A patent/CN1745050A/en active Pending
- 2004-01-27 JP JP2005504702A patent/JP4716868B2/en not_active Expired - Lifetime
- 2004-01-27 KR KR1020057014192A patent/KR20050097531A/en not_active Application Discontinuation
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- 2004-01-27 EP EP04705497A patent/EP1604949A2/en not_active Withdrawn
- 2004-01-27 WO PCT/JP2004/000678 patent/WO2004067446A2/en active Search and Examination
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Cited By (1)
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| CN114805376A (en) * | 2022-04-15 | 2022-07-29 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent material and organic electroluminescent device comprising same |
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|---|---|
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| US7435859B2 (en) | 2008-10-14 |
| TW200422281A (en) | 2004-11-01 |
| JP4716868B2 (en) | 2011-07-06 |
| WO2004067446A2 (en) | 2004-08-12 |
| WO2004067446A3 (en) | 2004-10-28 |
| KR20050097531A (en) | 2005-10-07 |
| JPWO2004067446A1 (en) | 2006-05-18 |
| US20060142370A1 (en) | 2006-06-29 |
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